TW201143960A - Low-temperature-sinterable bonding material, and bonding method using the bonding material - Google Patents

Low-temperature-sinterable bonding material, and bonding method using the bonding material Download PDF

Info

Publication number
TW201143960A
TW201143960A TW099139896A TW99139896A TW201143960A TW 201143960 A TW201143960 A TW 201143960A TW 099139896 A TW099139896 A TW 099139896A TW 99139896 A TW99139896 A TW 99139896A TW 201143960 A TW201143960 A TW 201143960A
Authority
TW
Taiwan
Prior art keywords
bonding
adhesive material
silver
temperature
adhesive
Prior art date
Application number
TW099139896A
Other languages
Chinese (zh)
Inventor
Keiichi Endoh
Yutaka Hisaeda
Akihiro Miyazawa
Aiko Nagahara
Toshihiko Ueyama
Original Assignee
Dowa Electronics Materials Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dowa Electronics Materials Co filed Critical Dowa Electronics Materials Co
Publication of TW201143960A publication Critical patent/TW201143960A/en

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B22F1/056—Submicron particles having a size above 100 nm up to 300 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/102—Metallic powder coated with organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J1/00—Adhesives based on inorganic constituents
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/06—Alloys based on silver
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
    • H01L21/52—Mounting semiconductor bodies in containers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/27—Manufacturing methods
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L24/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L24/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
    • H05K3/3457—Solder materials or compositions; Methods of application thereof
    • H05K3/3463—Solder compositions in relation to features of the printed circuit board or the mounting process
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2303/00—Functional details of metal or compound in the powder or product
    • B22F2303/10—Optional alloy component
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • H01L2224/29001—Core members of the layer connector
    • H01L2224/29099—Material
    • H01L2224/291—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof
    • H01L2224/29101—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof the principal constituent melting at a temperature of less than 400°C
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • H01L2224/29001—Core members of the layer connector
    • H01L2224/29099—Material
    • H01L2224/29198—Material with a principal constituent of the material being a combination of two or more materials in the form of a matrix with a filler, i.e. being a hybrid material, e.g. segmented structures, foams
    • H01L2224/29298—Fillers
    • H01L2224/29299—Base material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • H01L2224/29001—Core members of the layer connector
    • H01L2224/29099—Material
    • H01L2224/29198—Material with a principal constituent of the material being a combination of two or more materials in the form of a matrix with a filler, i.e. being a hybrid material, e.g. segmented structures, foams
    • H01L2224/29298—Fillers
    • H01L2224/29299—Base material
    • H01L2224/293—Base material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof
    • H01L2224/29338—Base material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
    • H01L2224/29339—Silver [Ag] as principal constituent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L2224/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
    • H01L2224/838—Bonding techniques
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/00013—Fully indexed content
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01004—Beryllium [Be]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01005—Boron [B]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01006—Carbon [C]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01019—Potassium [K]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01023—Vanadium [V]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01029—Copper [Cu]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01033—Arsenic [As]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01047—Silver [Ag]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/0105—Tin [Sn]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01078—Platinum [Pt]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01079—Gold [Au]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01082—Lead [Pb]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/013—Alloys
    • H01L2924/014—Solder alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/10—Details of semiconductor or other solid state devices to be connected
    • H01L2924/11—Device type
    • H01L2924/12—Passive devices, e.g. 2 terminal devices
    • H01L2924/1204—Optical Diode
    • H01L2924/12042—LASER
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/10—Details of semiconductor or other solid state devices to be connected
    • H01L2924/11—Device type
    • H01L2924/13—Discrete devices, e.g. 3 terminal devices
    • H01L2924/1301—Thyristor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/10—Details of semiconductor or other solid state devices to be connected
    • H01L2924/11—Device type
    • H01L2924/13—Discrete devices, e.g. 3 terminal devices
    • H01L2924/1301—Thyristor
    • H01L2924/13033—TRIAC - Triode for Alternating Current - A bidirectional switching device containing two thyristor structures with common gate contact
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/10—Details of semiconductor or other solid state devices to be connected
    • H01L2924/11—Device type
    • H01L2924/13—Discrete devices, e.g. 3 terminal devices
    • H01L2924/1304—Transistor
    • H01L2924/1305—Bipolar Junction Transistor [BJT]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/10—Details of semiconductor or other solid state devices to be connected
    • H01L2924/11—Device type
    • H01L2924/13—Discrete devices, e.g. 3 terminal devices
    • H01L2924/1304—Transistor
    • H01L2924/1305—Bipolar Junction Transistor [BJT]
    • H01L2924/13055—Insulated gate bipolar transistor [IGBT]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/10—Details of semiconductor or other solid state devices to be connected
    • H01L2924/11—Device type
    • H01L2924/13—Discrete devices, e.g. 3 terminal devices
    • H01L2924/1304—Transistor
    • H01L2924/1306—Field-effect transistor [FET]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/10—Details of semiconductor or other solid state devices to be connected
    • H01L2924/11—Device type
    • H01L2924/13—Discrete devices, e.g. 3 terminal devices
    • H01L2924/1304—Transistor
    • H01L2924/1306—Field-effect transistor [FET]
    • H01L2924/13091—Metal-Oxide-Semiconductor Field-Effect Transistor [MOSFET]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/151—Die mounting substrate
    • H01L2924/156—Material
    • H01L2924/157—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof
    • H01L2924/15738—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950 C and less than 1550 C
    • H01L2924/15747—Copper [Cu] as principal constituent
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0206—Materials
    • H05K2201/0224—Conductive particles having an insulating coating
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0242—Shape of an individual particle
    • H05K2201/0257—Nanoparticles
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/11—Treatments characterised by their effect, e.g. heating, cooling, roughening
    • H05K2203/1131—Sintering, i.e. fusing of metal particles to achieve or improve electrical conductivity

Abstract

Disclosed is a bonding material which enables the formation of a bonded article in a nitrogen atmosphere, can exhibit practically effective bonding strength without the need of carrying out any heat treatment procedure under pressurized or high-temperature conditions, and has reduced fluctuation in bonding between samples. The bonding material comprises: silver nanoparticles which have an average primary particle diameter of 1 to 200 nm and are coated with an organic substance having 8 or less carbon atoms; and a flux component which comprises a dispersion medium having a boiling point of 203 DEG C or higher and an organic substance having at least two carboxyl groups. Particularly preferably, a combination of silver nanoparticles and submicron silver particles is used.

Description

201143960 六、發明說明： 【發明所屬之技術領域】 本發明係關於黏合材料及使用其之黏合方、去 【先前技術】 隨諸如汽車、工業機器等所使用電子零件的大電流化，在 八内部所使用+導體的動作溫度有呈“的傾向。因而，迫 切期待能承受此種高溫環境的黏合材料。習知，雖使用在高 溫能維持強度的含料錫，但現今就從抑制料用的趨勢觀 之’更迫切渴望能提供適合此種條件的黏合方法。 能承受此種要求的黏合方法之候補，現今有著眼於在未使 用鉛的情況下’能於較塊體態銀更低溫的條件下進行黏合之 利用銀奈米粒子施行的黏合方法。在此種潮流中，除有提案 例如將氧化錄子與&quot;㈣騎齡㈣絲合材料的 方法(非專利文獻1與專利文獻υ之夕卜，尚有提案在將碳酸 銀或氧化銀、與銀奈米粒子進行混合的混合物中添加羧酸， 而形成黏合材料的方法（專利文獻2)。 [先前技術文獻] [專利文獻] 專利文獻1 :日本專利特開2009-267374號公報 專利文獻2 :日本專利特開2〇〇9-279649號公報 [非專利文獻] 非專利文獻1 ·守田等「使用微米尺寸氧化銀粒子在高溫環 099139896 3 201143960 境下的無錯黏合技術開發」，Ma㈣，帛49卷第&quot;虎 (2010) 【發明内容】 (發明所欲解決之問題） 如非專利文獻丄所揭示技術等中亦有記載般，通常利用此 種銀的黏合方法，當進行非屬少量吨合時必綠上部等處 施行加壓。在使用此種技術時’需要至少能同時施行加壓與 加熱的裝置，财難謂具通雜。又，亦會有僅能適用於里 有能承受加難度之機械強度的料問題。所以，若能提供 即使未施行加壓’仍可發揮適“合力雜膏，則可期待使 用對象能大幅擴大。 減:形成黏合體時的環境，因為至少在諸如大氣中會含 有乳的氧化環境中實施，因而會有因對黏合力造成不良影趣 U的界面部之銀遭氧化，而轉變為氧化銀的顧慮。特 係在微細衫财，此郷響可料_合強料將趨於明 合對象有考歧可燃性構件存在鄕合部分附近 ’月/亦有考慮必f在純環境下積極進行黏合。 下所二Γ純供錢域能騎此__氣之惰性環境 種糊、Γ分黏合力的黏合材料，便可期待能大幅擴大此 =、=用領域與可能性。又，在要求品質安定 亦必需降低試料(製品)間⑽合強度變動。 疋發明係提供：可在諸如氮的情性氣體令進行勘合 099139896 201143960 4成’且即便未施行加壓與高溫中的熱處理操力，仍可發 ==受實用的黏合強度，並可降低試料間之黏合變動的黏 (解決問題之手段） 發明者等為解決此種課題經深入鑽研，結果發現若為以下 =不黏合材料，即便在上㈣境下形絲合體，仍可發揮能 承受實用的強度，且可降低黏合變動，遂完成本案發明。 更具體而言’本發明的黏合_較佳係平均—次粒 1〜200nm，並含有：由石虔鉍s ,, __ …、 以下之有機物質所被覆的銀奈 - 米粒子、以及沸點達23〇t：以上的分散媒。 • 本發㈣黏合㈣，亦可更進―步含㈣均粒徑 〜3.〇μηι的銀粒子。 再者，本發明的黏合材料中，上述分散媒亦可更進 火點達loot：以上。 所再者，本發明的黏合材料亦可更進一步含有具嗎結的物 貝。而，該具有賴結的物質較佳係氧二乙酸(oxydlacetlc acid)。 再者，本發_黏合㈣較佳雜衫上述絲米粒子表 面的有機物中，至少一者係碳數為6。 ' #者’本發㈣提供❹上述黏合材料的黏合方法。具體 而呂，該黏合方法係相異二物f的黏合方法，包括有：㈣ 合面上塗佈至少含有彿點達2抓以上溶劑之黏合材料的 099139896 5 201143960 步驟（塗佈步驟）；在上述黏合材料上配置被黏合物的步驟； 在已配置上述被黏合物的狀態下，加熱至既定温度的預燒成 步驟；以及加熱至較上述預燒成溫度更高溫度的主燒成步 驟。 再者，本發明的黏合方法中，上述預燒成及上述主燒成的 步驟係可在惰性氣體環境下實施。 再者，本發明的黏合方法中，上述主燒成步驟係可依 200°C以上且500°C以下的溫度實施。 (發明效果） 藉由將如上述糊膏使用為黏合材料，便可獲得即使在惰性 環境中施行加熱時，仍具有高黏合強度、且降低試料間之黏 合強度變動的黏合體。 【實施方式】 本發明的黏合材料係含有銀奈米粒子與分散媒，較佳係依 更進一步含有銀粒子等的糊膏狀形態提供。以下針對本發明 黏合材料的構成成分進行詳細說明。另外，本發明的黏合材 料亦可簡稱「糊膏」。 &lt;銀奈米粒子&gt; 本發明所使用的銀奈米粒子係使用由穿透式電子顯微鏡 (TEM)照片所計算出，平均一次粒徑為1〜2〇〇nm、較佳為 1〜150nm、更佳為10〜l〇〇nm者。藉由使用具有此種粒徑的 粒子，便可形成具有強黏合力的黏合體。 099139896 6 201143960 利用穿透式電子顯微鏡進行的平均一次粒徑評估，係、仿^α 下順序貫施。首先’將經洗淨後的金屬奈米粒子2質量份， 添加於環己烷96質量份與油酸2質量份的混合溶液中，於 利用超音波使分散便獲得分散液。接著，將分散溶液滴下於 具支撐膜之Cu微電網上，經乾燥，便形成ΤΕΜ試料。將 所製成TEM試料使用穿透式電子顯微鏡（日本電子股份有 限公司製JEM-1 OOCXMark-ΙΙ型），依1 OOkV的加速電墨， 並以倍率300,000倍拍攝依明視野所觀察到的粒子影像。 粒子的平均一次粒徑亦可從依上述方法所獲得照片中，直 接利用游標卡尺等進行測定而求得，但亦可利用影像軟體進 行計算。此時的平均一次粒徑係針對TEM照片中的各個獨 立粒子至少測定200個，並依其數量平均計算出。 本發明所使用的銀奈米粒子係具有上述平均一次粒徑，且 表面被覆著有機物。該有機物較佳係使用總碳數在8以下 者。更佳係使用碳數在8以下，且具有一以上羧基者。具體 係可例示如下述物質，惟並不僅侷限於該等物質。例如：屬 於飽和脂肪酸的辛酸(caprylic acid)、庚酸(enanthic acid)、 己酸(caprrnc acid)、戊酸（吉草酸）、丁酸（酪酸）、丙酸 (propionic acid)等。又，就二羧酸係可舉例如：草酸、丙二 酸、曱基丙二酸、乙基丙二酸、琥⑽、甲基_酸、乙基 琥抬酸、苯基琥ί白酸、戊二酸、己二酸、庚二酸、辛二酸等。 就不飽和脂肪酸係可舉例如：山梨酸、順丁烯二酸等。 099139896 7 201143960 上述中’特別係若利用諸如己酸、庚酸、己二酸、山梨酸、 丙-酸等被覆著銀奈米粒子表面，便可輕易製造且依粉末形 悲獲付銀奈米粒子。即，由此種物質被覆著表面的粒子係在 保持一次粒子形態的情況下，進行凝聚便可輕易地回收。 又’當因低溫（未滿100。〇的情況而施加真空環境下的乾燥 操作時’便可依乾燥粒子回收。此時所獲得凝聚塊的大小係 就從至少能依JISP-3801的5種c之濾紙回收觀點，可謂需 達2.5μηι以上。 此現象係針對凝聚塊的大小，並非意味著其D5G達2·5μηι 以上。理由係若為d5〇值，無法利用濾紙進行過濾而是通過 的凝聚塊會變多，導致回收效率變差。俱是，因為本發明的 粒子並不會產生此種粒子通過情形，因而可確認濾'液能獲得 非為懸浮而是澄清的濾液，即，經由諸如己酸、庚酸、己二 酸、山梨酸、丙二酸所被覆的銀奈米粒子，亦可解釋為並非 平均值，而是具有至少2.5μιη程度大小的凝聚塊。所以，在 設計黏合材料時，最好使用由此程度大小的分子所被覆者。 而，該粒子係例如依照本說明書實施例中所記載的適當條件 進行糊膏化，便可獲得即使在回收時成為凝聚塊但仍會解 離’亦可利用點膠機等施行印刷塗佈的糊膏。 再者，亦可使用由複數有機物所被覆的銀奈米粒子、或亦 可併用具有不同平均一次粒徑的銀奈米粒子。 &lt;銀粒子&gt; 099139896 201143960 若除上述銀奈米粒子之外，尚添加次微米等級的銀粒子， 便可對更加提升黏合強度具貢獻。具體而言，較佳係使用平 均粒控達0.5μιη以上的銀粒子。本說明書的「平均粒徑計 异」’係依照以下順序根據雷射繞射法實施。首先，將銀粒 子試料0.3g裴入異丙醇5〇mL中，經利用輸出50W的超音 波;先/表機進行5分鐘而使分散後’再利用Microtrac粒度分 佈測定裝置(Haneywell日機裝製9320-X100)，依雷射繞射 法進行測定’將此時的D5Q(累積50質量％粒徑）值視為「平 均粒徑」。藉由併用此時的平均粒徑範圍為0.5〜3.0μπι、較 佳為0.5〜2.5μηι、更佳為0.5〜2 〇μιη範圍的粒子，便可提供 黏合力較高的黏合體。 此時，構成黏合材料的總成分中，含銀奈米粒子與銀粒子 的金屬成分比例係至少達8〇質量％以上、更佳係達85質量 %以上。若設為此金屬含有量範圍，當施行金屬化時便可確 保黏合強度’因而屬較佳。又，上限值係在％質量％以下。 當超過上限值時，雖可销齡強度，但有㈣出現強度變 動的傾向，因而非屬較佳。 &lt;分散媒&gt; 本發明形成糊膏態的黏合材料，係使銀奈綠子分散於分 政媒中。此時所使用的分散媒較佳係使用沸點達2机以 上、較佳係235t以上，不易弓丨發蒸發情況者。藉由使用此 種範圍内的溶劑’在主燒歧前面的階段+，溶劑便會揮 099139896 9 201143960 4便可降低Ά ’姆合賴與糊膏之接觸狀態發生變 動itu目為可降低黏合部的強度變動，因而屬較佳。 再者右〜1係有機溶劑，則引火點最好設為10〇〇c以 上、更佳達15吖以上、特佳達赋以上者。當引火點過 低時’因為該溶劑本身便料揮發，在保管時容易引火，因 而會伴隨有危險，n，故最_免。藉由設為上述範圍，便可 確保女王性’且適於取用的糊膏。 具上述性質的溶劑係藉由設為具2以上經基的物質，特別 係具2個羥基的二醇，尤其是碳數8以下的二醇，得知可同 時滿足適當的黏合強度與強度變動降低。其中，最好為具極 性的溶劑。 &lt;助炫劑成分&gt; 本發明的黏合材料中，除上述成分之外，尚可添加當作助 熔劑成分用的有機物。具體的係選擇具至少2個羧基的二羧 酸，更佳係選擇具醚鍵結且具至少2個羧基的二羧酸。藉由 選擇添加此種構造的物質，即使在氮中進行較低溫的熱處 理，仍可將由有機物所被覆的銀奈米粒子轉換為塊體態的 銀。 上述助熔劑成分亦是最好盡可能會分解為單純構造(具體 係最終形態為一氧化碳或水等）者。所以，較佳的有機物係 敢好僅由峡、氫、氧之類的元素構成。又，該分解溫度亦是 隶好至少在熱處理的設定溫度以下。藉由將分子量設定在 099139896 10 201143960 1〇00以下、較佳係5〇0以下、更佳係300以下，便更容易 產生分解或揮發，因而取用時的狀況佳。 上述助炫劑成分係可例示具有二㈣構造的甘醇酸。另 外，若分子過大，因為在進行分解時需要較高溫度，因而最 好避免。就㈣合強度提相觀點，助㈣W分最好在形成 黏合部之後，便進行分解並蒸散，而不會殘留於黏合部分 中。分解溫度最好係至少較低於主燒成時的設定溫度。具體 係選擇500°C以T、更佳係3〇〇。〇以下者。其中，當具有未 分解而直接氣化性質者的情況，上述「分解溫度」Μ稱為 「蒸發（氣化)溫度」。 更具體而言，分子構造中的合計碳數最多係在15以下、 較佳係在10以下。若屬於具此種程度碳數的構造，即使較 黏合溫度程度更低溫，仍可使分解或蒸散。 &lt;分散劑&gt; 本發明的糊f中，亦可添加能使銀奈米粒子粉末更加分散 的分散劑。藉由㈣此種分散劑，錢f中可確保粒子的獨 立性，且在祕舰分㈣奈錄Μ行反料能提高反應 性’可依更低溫形成均句的黏合體。此性質係在與粒子表面 間具親和性，且對分散媒亦具有·性的前提下，亦可使用 市售通用物。又，不僅可❹單獨種類，亦可併用使用。其 添加量係相對於糊膏全體在U)質量％以下、較佳係5質量 %以下、更佳係3質量％以下 099139896 11 201143960 具此種性質的分散劑代表物係有如：脂肪酸鹽（皂）、石黃 基脂肪酸酯鹽(MES)、烷基苯磺酸鹽(ABS)、直鏈烷基苯續 酸鹽(LAS)、烧基硫酸鹽(AS)、烧趟硫酸酯鹽(AES)、烧基硫 酸三乙醇等低分子陰離子性(anionic)化合物；或諸如脂肪酸 乙醇醯胺、聚氧化伸乙基烷醚(AE)、聚氧化伸乙基烷基苯醚 (APE)、山梨糖醇、山梨糖醇酐等低分子非離子系化合物； 或諸如烷基三曱銨鹽、二烷基二曱基氯化銨、烷基氯化吡啶 鑌等低分子陽離子性(cationic)化合物；或諸如烧羧基甜菜 鹼、磺甜菜鹼、卵磷脂等低分子兩性系化合物；或萘磺酸鹽 的曱醛縮合物、聚苯乙烯磺酸鹽、聚丙烯酸鹽、乙烯化合物 與羧酸系單體的共聚合體鹽、羧曱基纖維素、聚乙烯醇等所 代表的南分子水系分散劑；或諸如聚丙稀酸部分烧基g旨、聚 伸烧多元胺等高分子非水系分散劑；或諸如聚伸乙亞胺、甲 基丙烯酸胺烷基酯共聚合體等高分子陽離子系分散劑。但 是’在屬於適用於本發明粒子的前提下，並非排除具有此處 所例示形態物以外的構造物。 就分散劑若舉具體名稱已知有如下述物，但當具有上述性 質的情況，並非排除使用在本段中所記載物以外的物質。例 如：三洋化成股份有限公司製BEAULIGHT® LCA-H、 LCA-25NH等；共榮社化學股份有限公司製Flouren DOPA-15B等；日本Lubrizol股份有限公司製SOLPLUS® AX5、Solsperse 9000、Solthix 250 等、Efka Additives 公司 099139896 12 201143960 製 EFKA4008 等；Ajinomoto Fine-Techno 股份有限公司製 AJISPER PA111 等；Cognis Japan股份有限公司製 TEXAPHOR-UV21 等；BYK-Chemie . Japan 股份有限公司 製DisperBYK2020與BYK220S等；楠本化成股份有限公司 製 DISPARON® 1751N、HIPLAAD® ED-152 等；Neos 股份 有限公司製FTX-207S、FTERGENT® 212P等；東亞合成股 份有限公司製AS-1100等；花王股份有限公司製KAOCER® 2000、KDH-154、MX-2045L、HOMOGENOLL-18、RHEODOL SP-010V等；第一工業製藥股份有限公司製Epan U103、 SEANOL DC902B、NOIGEN EA-167、PLYSURF A219B 等； DIC股份有限公司製MEGAFAC®F-477等；曰信化學工業 股份有限公司製 SEALFAITH SAG503A、Dynol 604 等； Sannopco 股份有限公司製 SN Spurs 2180、SN Leveller S-906 等；AGC SEIMI CHEMICAL 公司製 S-386 等。 依此所形成的黏合材料係依照溶劑的種類、金屬比例之調 整，便可適當地變更其黏度。根據此現象，認為適當選擇印 刷方法係對能利用的用途擴大具貢獻。使對黏合對象地方的 塗佈較為容易。根據本發明者等的探討，常溫下係 10〜250Pa · S、較佳係10〜lOOPa · S、更佳係10〜50Pa · s左 右。另外’該黏度值係在25°C條件下，依5rpm使用C(錐)35/2 的測定值。 &lt;黏合材料(糊膏）之製造&gt; 099139896 13 201143960 根據本發明的黏合材料係經由大略如下述製造方法而提 供。例如銀奈綠子係可制日本專利第434侧號所記載 的銀奈米粒子。將依此所獲得銀奈米粒子、與具上述性質的 助熔以成分、以及視情況需要的分散劑，添加於上述分散媒 卜然後，導人於混賴泡機中，而形成該成分的混練物。 然後，依情況施行機械式分散處理而形成糊膏。 上械式分散處理時，在不致使銀奈米粒子產生明顯改 質的條件下，可使用公知任何方法。具體係可例示如：超音 波分散、分散機、三輥研磨機、球磨機、珠磨機、雙軸捏合 機自么轉式授拌機等，該等係可單獨使用、或併用複數。 &lt;黏合體之形成&gt; 黏合部之形成係在黏合物的黏合面上，利用例如金屬遮 罩2勝機或網版印刷法’將黏合材料塗佈呈厚2〇〜2〇〇pm 私度然後，黏貼上被黏合物，經加熱處理而將黏合材料施 行金屬化根據5亥黏合材料，雖即使在氮中的加熱處理仍可 金屬化’但即使在大氣中的加熱處理亦可金屬化。 此時，若使用本發明的黏合材料，即使未將黏合物與被黏 合物施行加壓，仍可形成黏合體。但是，並非排除施行加壓 的步驟。右追加將黏合物與被黏合物施行加壓的步驟，便可 將從銀奈米粒子或分散媒所產生的氣體更加脫除，因而屬較 佳。 原本的加壓係就從降低變動、提升黏合強度的觀點，通常 099139896 201143960 較佳係a又為高壓。俱疋，若使用本發明的糊膏，便未必需要 加壓。當視需要而施行加壓時，即便5MPa程度的加壓仍可 獲得充分的高黏合強度。 &lt;預燒成步驟&gt; 當使用本發明的黏合材料形成黏人 熱處理進行金屬化。具體係經由心广最好係利用多段 (預燒成步驟）之目的在於將黏合持料&quot;1冑帛W又^成 、十r所添加的溶劑予以 蒸發除ϋ練㈣溫施賴“，不伽齡被除去， 就連構成銀奈米粒子表面的㈣物亦會被除去。此情況，因 為黏合強度會變低、或會產生品質變動情形，因而最好避 免。具體係依未滿銀奈米粒子之分解溫度的溫度實施。 銀奈米粒子的分解溫度係依照被覆著其表_錢物或 分散媒、⑼加物，而會有頗大變化，因而最好預先利用諸 =TG測定等充分掌握該黏合材科的熱性質。一般，最好設 定為主燒成所設定溫度更低50〜4〇0&lt;^/右的低π产又 預燒成的時間係依存於其黏合對“二分二 右便已足夠，依情況亦會有30秒左士 工石的加熱便可的情況。 &lt;主燒成步驟&gt; ’將糊膏完全金屬化。 間中亦可設置升溫步 /秒、較佳係0.5〜5〇C/ 經由預燒成後，再利用主燒成步驟 在從預燒成步驟起至主燒成步驟的期 驟。此時的升溫速度係設為0.5〜lot 秒範圍内。 099139896 15 201143960 主燒成係在150 c以上且50(rc以下的溫度中保持6〇分鐘 以下、或30分鈿以下。本發明中雖未必需要施行加壓，但 在增加黏合強度、與降低黏合變動之目的下，亦可施行加 壓。此時所施行加壓的壓力係設定在1〇MPa以下，依情況 亦會有5MPa以下便已足夠的情形。 而，依此所獲得的％合體，即使在惰性環境下仍可獲得結 曰曰明顯成長。若具體的數值化，即便25〇。〇下進行1〇分鐘 的熱處理，依X射線的半值寬所計算出的Ag(111)面之結晶 粒徑，為65nm以上。因為該值越大，表示粒子間越不會有 結晶晶界產生，因而屬較佳。更佳係具有達67nm以上、特 佳係達70nm以上的性質者。 &lt;實施例&gt; &lt;銀奈米粒子之合成&gt; 在500mL燒杯中，使硝酸銀（東洋化學股份有限公司 製）13.4g溶解於純水72.1g中，而製得銀溶液。 接著’在5L燒杯中裝填入L34L纯水，藉由使氮通氣3〇 分鐘’而將溶存氧除去並使升溫至6〇ΐ。添加山梨酸(和光 純藥工業股份有限公司製）17.9g。接著，&amp; pH調整而添加 28%氨水（和光純藥工業股份有限公司製）2.82g。後述實施 例、比較例均係藉由該氨水添加而開始進行反應。在將其撥 拌的情況下’從反應開始起經5分鐘後，添加含水聯胺（純 度80%/大塚化學股份有限公司製)5.96g。 099139896 16 201143960 從開始反應起經9分鐘後，添加銀溶液而使進行反應。然 後，經30分鐘熟成，便形成由山梨酸所被覆的銀奈米粒子。 然後，利用No5C的濾紙施行過濾，再利用純水施行洗淨， 便獲得銀奈米粒子凝聚體。使該凝聚體在真空乾燥機中依 80 C、12小時的條件進行乾燥，便獲得銀奈米粒子乾燥粉 的凝聚體。 將經由上述方法所獲得的被覆山梨酸之銀奈米粒子凝聚 體乾燥粉（平均粒徑：60nm)45.0g，形成金屬微米粉，並將 球狀銀粒子粉末(DOWA電子股份有限公司製D2-1-C球狀 銀粉末·平均粒徑(D5〇)600nm)45.〇g、辛二醇（協和發酵化學 公司製：2-乙基-1，3-己二醇）9.〇g、以及濕潤分散劑的 BEAULIGHT® LCA-25NH(三洋化成股份有限公司 製）1.00g(相對於總糊膏重量為1.0%)進行混合，經利用混練 脫泡機(ΕΜΕ公司製V-mini300型）施行30秒鐘（混練條件 /Revolution ; 1400rpm、Rotation ; 700rpm)混練後，再利用 三輥(EXAKT Apparatebaus 公司製 22851Norderstedt 型）施 行五次來回(pass)，便製得黏合材料糊膏。將所獲得黏合材 料利用印刷法塗佈於基板上。此時的條件係設為金屬遮罩 (遮罩厚50jumt)、圖案係設為Mmm、厚5〇μπι、利用金屬擠 壓依手工印刷塗佈於經鑛銀的銅基板上。另外，辛二醇的彿 點係244°C，引火點係135°C。 將晶片（口2mm、厚2mm的銅基板)黏著於上述塗佈面上。 099139896 17 201143960 將依此所獲得黏晶利用爐（愛發科理工公司製桌上型燈加熱 裝置MILA-5000型），在氮壞境（氧濃度：5〇ppm以下）中施 行100°C、10分鐘加熱，藉此便將糊膏中的溶劑成分除去（預 燒成）。另外，為確認燒成膜的電阻率及燒結狀態，同時亦 製作在黏合材料上未載置晶片的情況下，僅將黏合材料印刷 於基板上並施行燒成的試料。 將預燒成的試料接著依升溫速度pc/秒的條件升溫至 350 C，經到達35(TC後再施行5分鐘加熱處理，便獲得黏 合體（主燒成）。在本實施例中預燒成、主燒成等二項步驟均 未施行加壓。 施打所獲得黏合體的黏合力確認。具體而言，根據 JISZ-03918-5 : 2003的「無鉛焊錫試驗方法第5部焊錫接 頭之拉伸及剪切試驗方法」所記載方法實施。即，將在基板 上黏合的被黏合體（晶片）朝水平方向按押，並測定承受按押 力導致黏合面出現斷裂時的力之方法。本實施例中，使用 DAGE公司製焊合測試儀（系列4〇〇〇)施行試驗。剪切高度係 150μηι，試驗速度係5mm/min，測定係依室溫實施。又，繞 成膜的電阻率係依四點探針法施行測定。 結果，實施例1的5樣品間之平均剪切強度係34 7Mh， 表示黏合變動的cv值(標準偏差/平均值)係141%。另外， 剪切試驗方法係直接測絲合©出現斷裂時的力(N)，依存 於黏合面積的值。此處為形成「格式化值」，便將所測得辦 099139896 201143960 裂時的力 除以黏合面積（本次 2 的情况係 2(mm)x2(mm)=4mm )的值(MPa)，設定為剪切強 、 ' 又。以下的 樣品亦同。 &lt;實施例2 &gt; 除將實施例1的糊膏構成，改為將被覆山梨酸之哿卉米；： 子凝聚體乾燥粉（平均粒徑：60nm)45.0g、金屬％ T、；&amp; 、&gt;蜀微米粉的球 狀銀粒子粉末(DOWA電子股份有限公司製D2 ' 球狀銀 粉末：平均粒徑(D5G)60〇nm)45.0g、辛二醇(協和發酵化學八 司製）8.9g、氧二乙酸〇.i〇g(相對於總糊膏重量為〇卜/)、 及濕潤分散劑的BEAULIGHT® LCA-25NH(三洋化成於以 有限公司製）1.00g(相對於總糊膏重量為j 〇%)進行混二77 外，其餘均重複實施例1的步驟。5樣品間的平均剪切強声 係47.1MPa’表示黏合變動的cv值係7 8%，相較於實施例 1之下’可獲得具有高黏合強度與低變動的黏合體。 &lt;實施例3〉 除將實施例2的糊膏構成，改為被覆山梨酸之銀奈米粒子 凝聚體乾燥粉44.2g、金屬微米粉的球狀銀粒子粉末44&amp;、 及辛二醇(協和發酵化學公司製）1〇 5§之外’其餘均同樣的 重複實施例2的步驟。所獲得黏合體的黏合強度及表示變動 的CV值，如表1所示。 &lt;實施例4&gt; 除將實施例1的糊膏構成，改為減山梨社銀奈米粒子 099139896 19 201143960 凝聚體乾燥粉的平均粒請nm之外，其餘均設為相同的 構成比例’並重複實施例丨的步驟。所獲得黏合體的黏合強 度及表示變動的CV值，如表1所示。 &lt;實施例5 &gt; 除將實施例4的糊膏構成，由辛二醇9如改為辛二醇 8.95g與氧二乙酸0.05g(相對於總糊膏重量為〇 〇5%)之外， 其餘均重複實施例4的步驟。所獲得點合體的黏合強度及表 示變動的CV值’如表1所示。 &lt;實施例6&gt; 除將實施例4的糊膏構成，改為被覆山梨酸之銀奈米粒子 凝聚體乾燥粉46.0g、金屬微米粉的球狀銀粒子粉末46化、 及辛二醇(協和發酵化學公司製)7.〇g之外，其餘均同樣的重 複實施例4的步驟。所獲得黏合體的黏合強度及表示變動的 CV值，如表1所示。 &lt;實施例7&gt; 除將貫施例4的糊膏構成，改為被覆山梨酸之銀奈米粒子 凝聚體乾燥粉43.〇g、金屬微米粉的球狀銀粒子粉末43如、 辛二醇(協和發酵化學公司製以及氧二乙酸0.10g(相 對於總糊膏重里為G.1G%)之外，其餘均重複實施例4的步 驟。所獲得黏合體的黏合強度及表示變動的…值，如表】 所示。 &lt;實施例8&gt; 099139896 20 201143960 除將實施例4的糊膏構成，改為被覆山梨酸之銀奈米粒子 凝聚體乾燥粉44.2g、金屬微米粉的球狀銀粒子粉末44.2g、 辛一醇（協和發酵化學公司製）l〇.5g、以及氧二乙酸o.l〇g(相 對於總糊膏重量為〇.10%)之外，其餘均重複實施例4的步 驟。所獲得黏合體的黏合強度及表示變動的CV值，如表1 所示。又，當將主燒成的溫度設為26〇°c，並施行1〇分鐘 加熱時，獲得黏合強度22.1MPa、CV值22.4%的結果。 &lt;比較例1 &gt; 除將實施例1的糊膏構成，改為被覆山梨酸之銀奈米粒子 政聚體乾燥粉(平均粒徑：6Gnm)45.Gg、金屬微米粉的球狀 銀粒子粉末(DOWA電子股份有限公司製⑽小c球狀銀粉 末.平均粒徑(D5〇)60〇nm)45.0g、以及松油醇(結構異構物混 合/和光純藥工業股份有限公司製）9.〇〇g之夕卜，其餘均重複 實施例1的步驟。5樣品間的平均剪切強度係25 5咖，表 示黏合變動的CV值係30.6%，相較於實施例}之下’成^ 黏合強度較低、變動較大的黏合體。另外，松油醇的沸 219°C、引火點係91°C。 ' &lt;比較例2&gt; 除將比較例1的松油醇(結構異構物混合/和光純藥工業股 份有限公司製)9.GGg改為松油醇(結構異構物混合/和光純藥 工業股份有限公司製）8.80g、以及氧二乙酸〇2〇g(相對於總 糊膏重量為G.2%)之外，其餘均重複比較例丨的步驟。所獲 099139896 21 201143960 得黏合體的黏合強度及表示變動的cv值，如表1所示 &lt;比較例3&gt; 除將比較例1的松鱗(結構異構物混合/和光純藥工業股 份有限公司製)9.00g改為松油醇(結構異構物混合/和光純藥 工業股份有限公司製)8.90g、以及氧二乙酸Q叫(相對於總 糊膏重量為G.1%)之外’其餘均重複比較例丨的步驟。所獲 得黏合體的黏合強度及表示變動的cv值，如表丨所示。 &lt;比較例4&gt; 除將實施例4的辛二醇變更為松㈣(結構異構物混合/和 光純藥4股份㈣公—）之外，其餘均鍾實施例4的 步驟。所獲得黏合體的黏合強度及表示變動的cV值，如表 1所示。 [表1] 銀粉 溶劑 氧二 乙酸 (g) 山梨酸(g) 微米粉 (g) 松油醇（g) :沸點219°C 分散劑 黏合 強度 (MPa) CV 60nm lOOnm 辛二醇(g) :沸點244°C (g) (%) 實施例1 實施例2 tWmz - -- -- -- -- 實施例4 ------------ 45.0 .......... 45.0 9.00 1.00 34.7 14.1 45.0 .......... 45.0 47.1 7 S 44.2 .......... 42.0 9 V 45.0 45.0 44.9 17 S X苑例5 ----- 1 45.0 50.0 6 S %ΡΜίβ. -- 46.0 49.6 10 S 貫施例7 實施例8 ^較例1 tbKj'2 ........ 43.0 33.1 *&gt; -i 44.2 10.50 0.10 1.00 42.7 8.1 45.0 45.0 9.00 1.00 25.5 30.6 45.0 -______ .8.80 24.7 M 4 比較例3 tbfe^j*4 45.0 8.90 31.4 HI 0 9.00 1.00 29.8 12.8 099139896 22 201143960 若將比杈例1與貫施例1進行比較，得知將溶劑從松油醇 (沸點219 C)變更為辛二醇（沸點244它）的效果。由此得知可 狻得黏合強度較高、且將降低黏合樣品間之強度變動者。 又，若將辛二醇其中一部分取代為氧二乙酸，可獲得黏合強 度較高、且經降低變動的黏合體，此現象利用實施例丨與2 的比較便可得知。 藉由比較例1與比較例4的比較，得知依照粒徑不同（從 60nm變更為100nm)所產生的效果。藉此，得知可獲得黏合 強度略獲改善、且黏合樣品間的強度變動已降低者。藉由比 較例4與實施例4的比較，得知變更溶劑的效果，但黏合樣 品間的強度變動係同等’可獲得黏合強度獲明顯改善者。 又，若將辛二醇其中一部分取代為氧二乙酸，便可獲得黏合 強度較尚、且經降低變動的黏合體，此現象係可由實施例4 與5的比較得知。 由該等得知當使用實施例的糊膏時，無關是否在氮中進行 燒成，均可獲得黏合強度高達3〇MPa以上、且黏合強度變 動未滿20%者。此對製品安定性的提升具明顯貢獻。 再者，實施例5中測得黏度為71.5MPa、實施例7中測得 黏度為2 8.5 Μ P a ’得知依照金屬的構成可提供適度黏度的糊 烏。此現象係可提供具有配合各種印刷方式之黏度的糊膏， 可期待能適用於所有用途的黏合。 (產業上之可利用性） 099139896 23 201143960 就從以上事項得知，依照本案發明的黏合，係可應用於非 絕緣型半導體裝置、裸晶安裝組裝的技術，亦可應用於諸如 功率裝置(IGBT、整流二極體、功率電晶體、功率MOSFET、 絕緣閘雙極性電晶體、閘流體、閘控開關閘流體、雙向閘流 體製造時的黏合步驟。又，亦可使用為表面經鉻處理過的玻 璃之黏合材料，亦可利用為使用LED的照明裝置之電極、 與框架之黏合材料。 【圖式簡單說明】 圖1為實施例與比較例的黏合強度(MPa)與樣品間變動 CV值(％)的圖。 099139896 24201143960 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a bonding material and a bonding method using the same, and [previously] with a large current of electronic components used in automobiles, industrial machines, etc. There is a tendency for the operating temperature of the +conductor to be used. Therefore, an adhesive material capable of withstanding such a high-temperature environment is eagerly expected. It is known that a tin containing material capable of maintaining strength at a high temperature is used, but it is now used for suppressing materials. The trend view is more eager to provide a bonding method suitable for this condition. The candidate for bonding methods that can withstand such requirements now has the advantage of being able to lower the temperature of the bulk silver in the absence of lead. A bonding method using silver nanoparticles for bonding. In this trend, there are proposals, for example, a method of oxidizing a recording and &quot;(4) aging (four) silking materials (Non-Patent Document 1 and Patent Literature) In addition, there is a proposal to add a carboxylic acid to a mixture of silver carbonate or silver oxide and silver nanoparticles to form a bonding material. [Patent Document 2] [Prior Art Document] [Patent Document] Patent Document 1: Japanese Patent Laid-Open No. 2009-267374 Patent Document 2: Japanese Patent Laid-Open Publication No. Hei No. Hei. 1 · Shou Tian et al. "Development of error-free adhesion technology using micron-sized silver oxide particles in high temperature ring 099139896 3 201143960", Ma (4), 帛 49 volume &quot;虎 (2010) [Summary of the invention] (Problems to be solved by the invention) As described in the technique disclosed in the non-patent document, the silver bonding method is generally used, and when it is not a small amount of tonnage, it is required to pressurize the upper part of the green, etc. When using this technique, it is required. At least the device for pressurization and heating can be applied at the same time, and the financial trouble is said to be complicated. Moreover, there is a problem that it can only be applied to the material that can withstand the mechanical strength of the difficulty. Therefore, if it is not provided, no pressure is applied. 'You can still use the Heli paste, you can expect to increase the use of the object. Reduction: The environment in which the adhesive is formed, because at least in an oxidizing environment such as the atmosphere containing milk, there is a cause Adhesive force causes the silver in the interface part of the bad shadow U to be oxidized, and it turns into the concern of silver oxide. The special line is in the micro-shirt, which can be expected to be commensurate with the flammability of the object. The components exist in the vicinity of the fitting part. 'Monthly, there are also considerations that must be actively bonded in a pure environment. The next two pure water supply fields can ride this __ inert gas environment, paste adhesive force bonding materials, It can be expected to greatly expand the area and possibility of this =, = use. In addition, it is necessary to reduce the strength of the joint strength between the samples (products) in order to ensure the quality stability. 疋Inventory provides: can be carried out in an inert gas such as nitrogen察合099139896 201143960 4成' and even if the heat treatment in the pressurization and high temperature is not applied, it can still be issued == the practical adhesive strength, and the viscosity of the adhesion between the samples can be reduced (the means to solve the problem). In order to solve such a problem, it has been found that the following = non-adhesive material, even in the case of the upper (four) shape of the wire, can still withstand the practical strength, and can reduce the adhesion change, and completed the invention. More specifically, the adhesive of the present invention is preferably an average of -1 to 200 nm, and contains: a silver-n-particle coated with an organic substance of the following sarcophagus s , , _ _ ..., and a boiling point 23〇t: The above dispersion medium. • This (4) bond (4), can also be further stepped into (four) silver particles with a particle size of ~3.〇ηηι. Further, in the adhesive material of the present invention, the above-mentioned dispersion medium may have a more fire point of loot: or more. Further, the adhesive material of the present invention may further contain a material having a knot. However, the substance having a lysate is preferably oxydlacetlc acid. Further, in the present invention, at least one of the organic substances on the surface of the silk rice particles has a carbon number of 6. '#者' This issue (4) provides a bonding method for the above-mentioned adhesive materials. Specifically, the bonding method is a bonding method of the different materials f, including: (4) a step of coating the bonding material containing at least 2 points of the solvent of the solvent to the surface of the bonding material (099139896 5 201143960) (coating step); a step of disposing a binder on the binder; a pre-firing step of heating to a predetermined temperature in a state in which the binder is disposed; and a main calcination step of heating to a temperature higher than the pre-baking temperature. Further, in the bonding method of the present invention, the pre-baking and the main firing step may be carried out under an inert gas atmosphere. Further, in the bonding method of the present invention, the main baking step may be carried out at a temperature of 200 ° C or more and 500 ° C or less. (Effect of the Invention) By using the above-mentioned paste as a binder, it is possible to obtain an adhesive which has high adhesive strength and reduces the change in the adhesive strength between the samples even when heated in an inert environment. [Embodiment] The binder of the present invention contains silver nanoparticles and a dispersion medium, and is preferably provided in a paste form containing silver particles or the like. The constituent components of the adhesive material of the present invention will be described in detail below. Further, the adhesive material of the present invention may also be referred to simply as "paste". &lt;Silver Nanoparticles&gt; The silver nanoparticles used in the present invention are calculated from a transmission electron microscope (TEM) photograph, and have an average primary particle diameter of 1 to 2 nm, preferably 1 to 1. 150 nm, more preferably 10 to l 〇〇 nm. By using particles having such a particle diameter, an adhesive having a strong adhesive force can be formed. 099139896 6 201143960 The average primary particle size evaluation using a transmission electron microscope is performed sequentially. First, 2 parts by mass of the washed metal nanoparticles were added to a mixed solution of 96 parts by mass of cyclohexane and 2 parts by mass of oleic acid to obtain a dispersion by dispersing with ultrasonic waves. Next, the dispersion solution was dropped on a Cu microgrid having a support film, and dried to form a ruthenium sample. A TEM sample prepared by using a transmission electron microscope (JEM-1 OOCXMark-ΙΙ type manufactured by JEOL Ltd.), an accelerated ink of 100 volts, and a particle observed at a magnification of 300,000 times. image. The average primary particle diameter of the particles can also be obtained by directly measuring with a vernier caliper or the like from the photograph obtained by the above method, but it can also be calculated by using the image software. The average primary particle diameter at this time was measured at least 200 for each individual particle in the TEM photograph, and was calculated on the basis of the number. The silver nanoparticles used in the present invention have the above average primary particle diameter and are coated with an organic substance. The organic substance is preferably one having a total carbon number of 8 or less. More preferably, those having a carbon number of 8 or less and having one or more carboxyl groups are used. Specifically, the following substances are exemplified, but are not limited to the substances. For example, caprylic acid, enanthic acid, caprrnc acid, valeric acid (jimic acid), butyric acid (butyric acid), propionic acid, and the like which are saturated fatty acids. Further, examples of the dicarboxylic acid system include oxalic acid, malonic acid, mercaptomalonic acid, ethylmalonic acid, succinic acid (10), methyl-acid, ethyl succinic acid, and phenyl succinic acid. Glutaric acid, adipic acid, pimelic acid, suberic acid, and the like. Examples of the unsaturated fatty acid include sorbic acid and maleic acid. 099139896 7 201143960 The above-mentioned special system can be easily manufactured and used to pay silver nanoparticles according to the shape of powder if it is coated with the surface of silver nanoparticles by using, for example, caproic acid, heptanoic acid, adipic acid, sorbic acid, propionic acid or the like. particle. That is, the particles coated on the surface by such a substance can be easily collected by aggregating while maintaining the primary particle form. In addition, when it is subjected to a low temperature (drying operation under a vacuum environment of less than 100 〇, it can be recovered by dry particles. The size of the agglomerates obtained at this time is at least 5 types according to JISP-3801. c filter paper recycling point of view, can be said to be more than 2.5μηι. This phenomenon is based on the size of the agglomerate block, does not mean that its D5G is more than 2·5μηι. The reason is that if the d5 〇 value, can not be filtered by filter paper but passed The number of agglomerates increases, resulting in poor recovery efficiency. Since the particles of the present invention do not produce such particles, it is confirmed that the filtrate can obtain a filtrate that is not suspended but clarified, that is, via Silver nanoparticles coated with, for example, caproic acid, heptanoic acid, adipic acid, sorbic acid, malonic acid, may also be interpreted as not being average values, but having agglomerates having a size of at least 2.5 μηη. Therefore, in designing the bonding In the case of a material, it is preferred to use a molecule of this size to be coated. However, the particle can be obtained, for example, in accordance with the appropriate conditions described in the examples of the present specification. In the case of agglomerates, they may still be dissociated. It is also possible to apply a paste applied by a dispenser or the like. Further, silver nanoparticles coated with a plurality of organic substances may be used, or a different average primary particle may be used in combination. Silver nanoparticles of the diameter. &lt;Silver particles&gt; 099139896 201143960 In addition to the silver nanoparticle described above, the addition of submicron-sized silver particles can contribute to further improvement of the bonding strength. The silver particles having an average particle size of 0.5 μm or more are used. The "average particle size difference" in the present specification is carried out according to the following procedure in accordance with the laser diffraction method. First, 0.3 g of the silver particle sample is poured into the isopropanol 5 In 〇mL, the ultrasonic wave of 50W is output, and the first time/fibrate is used for 5 minutes to make the dispersion. The microtrac particle size distribution measuring device (Haneywell Japanese machine equipped 9320-X100) is used for measurement by laser diffraction method. The D5Q (accumulated 50% by mass particle diameter) value at this time is regarded as the "average particle diameter." The average particle diameter range at this time is 0.5 to 3.0 μm, preferably 0.5 to 2.5 μm, more preferably 0.5~2 〇μιη range In this case, the binder having a high adhesive strength can be provided. In this case, the ratio of the metal component of the silver-containing nanoparticle to the silver particle is at least 8% by mass or more, and more preferably 85. If the metal content is within the range of the metal content, the adhesion strength can be ensured when the metallization is performed. Therefore, the upper limit value is less than or equal to the % by mass. Although the strength of the age is small, there is a tendency to change the intensity (4), which is not preferable. <Dispersion Medium> The present invention forms a paste-like adhesive material in which the silver chlorophyll is dispersed in a sub-government medium. The dispersing medium to be used preferably has a boiling point of 2 or more, preferably 235 or more, and is not easily evaporating. By using a solvent in this range 'in the stage before the main burn-in, the solvent will be reduced by 099139896 9 201143960 4 Ά 'The change of the contact state of the M-May and the paste can reduce the adhesion. The intensity of the change is therefore preferred. Further, the right ~ 1 series organic solvent, the ignition point is preferably set to 10 〇〇 c or more, more preferably 15 吖 or more, and more than the best. When the ignition point is too low, the solvent itself is volatilized, and it is easy to ignite during storage. Therefore, there is a danger, n, so the most is free. By setting it as the above range, it is possible to ensure a queen's taste and a paste suitable for use. The solvent having the above properties is a diol having two or more hydroxyl groups, particularly a diol having two hydroxyl groups, particularly a diol having a carbon number of 8 or less, and it is known that the adhesive strength and strength can be appropriately satisfied at the same time. reduce. Among them, it is preferred to have a polar solvent. &lt;Promoting Agent Component&gt; In the binder of the present invention, in addition to the above components, an organic substance as a flux component may be added. Specifically, a dicarboxylic acid having at least two carboxyl groups is selected, and a dicarboxylic acid having an ether bond and having at least two carboxyl groups is more preferred. By selecting a substance to which such a structure is added, even if a lower temperature heat treatment is performed in nitrogen, the silver nanoparticle coated with the organic substance can be converted into bulk silver. The above-mentioned flux component is also preferably decomposed as much as possible into a simple structure (specifically, the final form is carbon monoxide or water). Therefore, the preferred organic matter is composed of only elements such as gorge, hydrogen, and oxygen. Further, the decomposition temperature is also at least below the set temperature of the heat treatment. When the molecular weight is set to 099139896 10 201143960 1 00 or less, preferably 5 Å or less, more preferably 300 or less, decomposition or volatilization is more likely to occur, so that the condition at the time of use is good. The above-mentioned builder component can be exemplified by a glycolic acid having a di(tetra) structure. In addition, if the molecule is too large, it is best to avoid because it requires a higher temperature for decomposition. In view of the (4) combined strength, the W (W) W is preferably decomposed and evaporated after forming the bonded portion, and does not remain in the bonded portion. The decomposition temperature is preferably at least lower than the set temperature at the time of main firing. Specifically, it is selected at 500 ° C to T, and more preferably 3 〇〇. 〇 The following. Among them, in the case of having a direct gasification property which is not decomposed, the above "decomposition temperature" is referred to as "evaporation (gasification) temperature". More specifically, the total carbon number in the molecular structure is at most 15 or less, preferably 10 or less. If it is a structure with such a carbon number, decomposition or evapotranspiration can be caused even if the bonding temperature is lower. &lt;Dispersant&gt; In the paste f of the present invention, a dispersant capable of further dispersing the silver nanoparticle powder may be added. With (4) such a dispersant, the independence of the particles can be ensured in the money f, and the reactivity can be improved in the case of the secret ship (4), which can form a binder of a uniform sentence at a lower temperature. This property is also a commercially available general product under the premise that it has affinity with the surface of the particles and also has a property for the dispersion medium. Moreover, it is possible to use not only individual types but also together. The amount of addition is based on U) mass% or less, preferably 5% by mass or less, more preferably 3% by mass or less based on the entire paste. 099139896 11 201143960 A dispersant representative having such a property is, for example, a fatty acid salt (soap) ), sulphate-based fatty acid ester salt (MES), alkyl benzene sulfonate (ABS), linear alkyl benzoate (LAS), alkyl sulphate (AS), sulphuric acid sulphate (AES) a low molecular anionic compound such as triethyl sulphate; or such as fatty acid decylamine, polyoxyalkylene ether (AE), polyoxyethylidene ether (APE), sorbose a low molecular nonionic compound such as an alcohol or sorbitan; or a low molecular cationic compound such as an alkyltriammonium salt, a dialkyldicylidene ammonium chloride or an alkylpyridinium chloride; or a low molecular amphoteric compound such as a carboxybetaine, a sulfobetaine or a lecithin; or a furfural condensate of a naphthalenesulfonate, a polystyrene sulfonate, a polyacrylate, a vinyl compound and a carboxylic acid monomer; Southern molecular water system represented by copolymer salt, carboxymethyl cellulose, polyvinyl alcohol, etc. a dispersing agent; or a polymer non-aqueous dispersing agent such as a polyacrylic acid moiety, a polycondensation polyamine, or a polymer cation dispersion such as a polyethylenimine or an aminoalkyl methacrylate copolymer; Agent. However, the structure other than the ones exemplified herein is not excluded on the premise that it is suitable for the particles of the present invention. The following description of the dispersing agent is known as the following, but in the case of having the above properties, the substances other than those described in the paragraph are not excluded. For example: BEAULIGHT® LCA-H, LCA-25NH, etc. manufactured by Sanyo Chemical Co., Ltd.; Flouren DOPA-15B manufactured by Kyoeisha Chemical Co., Ltd.; SOLPLUS® AX5, Solsperse 9000, Solthix 250, etc. by Lubrizol Co., Ltd., Japan Efka Additives Company 099139896 12 201143960 EFKA4008, etc.; AJISPER PA111 manufactured by Ajinomoto Fine-Techno Co., Ltd.; TEXAPHOR-UV21 manufactured by Cognis Japan Co., Ltd.; BYK-Chemie. DisperBYK2020 and BYK220S manufactured by Japan Co., Ltd.; DISPARON® 1751N, HIPLAAD® ED-152, etc.; FTX-207S and FTERGENT® 212P manufactured by Neos Co., Ltd.; AS-1100 manufactured by Toagosei Co., Ltd.; KAOCER® 2000, KDH- by Kao Co., Ltd. 154, MX-2045L, HOMOGENOLL-18, RHEODOL SP-010V, etc.; Epan U103, SEANOL DC902B, NOIGEN EA-167, PLYSURF A219B, etc. manufactured by Daiichi Industrial Co., Ltd.; MEGAFAC® F-477, etc. manufactured by DIC Corporation ; SEALFAITH SAG503A, Dynol 604, etc. manufactured by Yuxin Chemical Industry Co., Ltd.; Sannopco shares Co., Ltd. SN Spurs 2180, SN Leveller S-906, etc.; AG-SEIMI CHEMICAL company S-386. The adhesive material thus formed can be appropriately changed in viscosity depending on the type of the solvent and the metal ratio. Based on this phenomenon, it is considered that the proper selection of the printing method contributes to the expansion of the usable use. It is easier to apply the place to be bonded. According to the investigation by the inventors of the present invention, it is 10 to 250 Pa·s at room temperature, preferably 10 to 100 Pa·s, and more preferably 10 to 50 Pa·s. Further, the viscosity value was measured at 25 ° C using a measured value of C (cone) 35/2 at 5 rpm. &lt;Manufacture of adhesive material (paste)&gt; 099139896 13 201143960 The adhesive material according to the present invention is provided by a manufacturing method substantially as follows. For example, the silver nanoparticle system can be made of the silver nanoparticle described in Japanese Patent No. 434. The silver nanoparticle obtained in accordance with the above, a fluxing component having the above properties, and a dispersing agent as needed are added to the above dispersion medium, and then introduced into the mixing machine to form the component. Mixtures. Then, mechanical dispersion treatment is performed as appropriate to form a paste. In the case of the mechanical dispersion treatment, any known method can be used without causing significant deterioration of the silver nanoparticles. Specifically, for example, an ultrasonic dispersion, a dispersing machine, a three-roll mill, a ball mill, a bead mill, a twin-shaft kneader, a rotary mixer, or the like can be exemplified, and these may be used singly or in combination. &lt;Formation of Adhesives&gt; The formation of the adhesive portion is on the adhesive surface of the adhesive, and the adhesive material is coated to a thickness of 2 〇 2 〇〇 pm by, for example, a metal mask 2 or a screen printing method. Then, the adherend is adhered, and the adhesive material is metallized by heat treatment. According to the 5H bonding material, although it can be metalized even by heat treatment in nitrogen, it can be metalized even in the heat treatment in the atmosphere. At this time, if the adhesive material of the present invention is used, the adhesive can be formed even if the adhesive and the adhesive are not pressurized. However, the step of applying pressure is not excluded. It is preferable to add a step of pressurizing the binder and the binder to the right to remove the gas generated from the silver nanoparticles or the dispersion medium. The original pressurization system is generally a high pressure from the viewpoint of reducing the variation and improving the bonding strength, usually 099139896 201143960. Moreover, if the paste of the present invention is used, it is not necessary to pressurize. When pressurization is carried out as needed, a sufficient high adhesive strength can be obtained even under a pressure of about 5 MPa. &lt;Pre-sintering step&gt; Metallization is carried out by forming an adhesive heat treatment using the adhesive material of the present invention. Specifically, it is best to use multiple sections (pre-sintering step) through Xinguang. The purpose of the method is to evaporate and remove the solvent added by the adhesive holding material &quot;1胄帛W and ^, and ten ("Wen Shi Lai" If the gamma age is removed, even the (4) material that forms the surface of the silver nanoparticles will be removed. In this case, because the bonding strength will be low or the quality will change, it is best to avoid it. The temperature at which the decomposition temperature of the nanoparticles is carried out is carried out. The decomposition temperature of the silver nanoparticles is greatly changed depending on the surface of the material, the dispersion medium, and the (9) addition, and it is preferable to use the TG in advance. It is necessary to fully grasp the thermal properties of the adhesive material. Generally, it is better to set the temperature set lower for the main firing to 50~4〇0&lt;^/right. The low π production and pre-burning time depend on the bonding pair. "Two points and two right is enough. According to the situation, there will be 30 seconds of heating of the Zuo Shigong stone. &lt;Main baking step&gt; 'The paste is completely metallized. The heating step/second may be provided, preferably 0.5 to 5 〇C/ after the pre-firing, and then the main firing step is used from the pre-baking step to the main firing step. The temperature increase rate at this time is set to be in the range of 0.5 to 1 second. 099139896 15 201143960 The main firing system is maintained at 150 c or more and 50 (temperature below rc for 6 minutes or less, or 30 minutes or less. In the present invention, although it is not necessary to apply pressure, the bonding strength is increased and the bonding is lowered. For the purpose of the change, the pressurization may be performed. The pressure at which the pressurization is performed is set to be less than 1 MPa, and depending on the case, it may be sufficient if it is 5 MPa or less. However, the % fit obtained according to this, Even in an inert environment, the growth of the crucible can be obtained. If it is specifically numerical, even 25 〇. The heat treatment for 1 minute is carried out, and the Ag(111) surface calculated by the half-value width of the X-ray is used. The crystal grain size is 65 nm or more. Since the larger the value, the crystal grain boundary is not formed between the particles, which is preferable, and more preferably, it has a property of 67 nm or more and a particularly good system of 70 nm or more. (Examples) &lt;Synthesis of Silver Nanoparticles&gt; In a 500 mL beaker, 13.4 g of silver nitrate (manufactured by Toyo Chemical Co., Ltd.) was dissolved in 72.1 g of pure water to obtain a silver solution. Fill the beaker with L34L pure water, borrow The nitrogen was purged for 3 minutes, and the dissolved oxygen was removed and the temperature was raised to 6 Torr. 17.9 g of sorbic acid (manufactured by Wako Pure Chemical Industries, Ltd.) was added. Next, & pH adjustment was added to add 28% aqueous ammonia (and pure light). 2.82 g manufactured by Pharmaceutical Industries, Ltd. The examples and comparative examples described below were started by the addition of the ammonia water. In the case of mixing, 'addition of aqueous hydrazine after 5 minutes from the start of the reaction (purity: 80%/manufactured by Otsuka Chemical Co., Ltd.) 5.96 g. 099139896 16 201143960 After 9 minutes from the start of the reaction, a silver solution was added to carry out the reaction, and then, after 30 minutes of aging, a sorbic acid was formed. Silver nanoparticles were filtered by No5C filter paper and washed with pure water to obtain silver nanoparticle aggregates. The aggregates were dried in a vacuum dryer under conditions of 80 C for 12 hours. The aggregate of the silver nanoparticle dry powder was obtained. 45.0 g of the coated sorbic acid silver nanoparticle aggregate dry powder (average particle diameter: 60 nm) obtained by the above method was formed to form a metal microparticle. Powder, and spherical silver particle powder (D2-1-C spherical silver powder manufactured by DOWA Electronics Co., Ltd., average particle diameter (D5〇) 600 nm) 45. 〇g, octanediol (manufactured by Kyowa Fermentation Chemical Co., Ltd.: 2-ethyl-1,3-hexanediol) 9. 〇g, and a wet dispersant of BEAULIGHT® LCA-25NH (manufactured by Sanyo Chemical Co., Ltd.) 1.00 g (1.0% based on the total paste weight) The mixture was mixed and kneaded for 30 seconds (mixing conditions/Revolution; 1400 rpm, Rotation; 700 rpm) by a kneading defoaming machine (manufactured by Konica Minolta Co., Ltd.), and then three rolls (22,851 Nordstedt type manufactured by EXAKT Apparatebaus Co., Ltd.) were used. The pass material is used to make a paste of adhesive material. The obtained adhesive material was applied onto the substrate by a printing method. The conditions at this time were set to a metal mask (mask thickness: 50 jumt), a pattern of Mmm, and a thickness of 5 μm, and were applied by hand-printing onto a silver-plated copper substrate by metal extrusion. Further, the octanediol has a point of 244 ° C and a fire point of 135 ° C. A wafer (a copper substrate having a thickness of 2 mm and a thickness of 2 mm) was adhered to the coated surface. 099139896 17 201143960 The obtained crystal-using furnace (the MILA-5000 type of table lamp heating device manufactured by Aiko Science and Technology Co., Ltd.) is used, and 100 ° C is applied in a nitrogen atmosphere (oxygen concentration: 5 〇 ppm or less). The solvent component in the paste was removed (pre-baked) by heating for 10 minutes. Further, in order to confirm the electrical resistivity and the sintered state of the fired film, and also when the wafer was not placed on the adhesive material, only the adhesive material was printed on the substrate and the sample was fired. The pre-fired sample was further heated to 350 C under the conditions of a temperature increase rate of pc/sec, and after reaching 35 (TC and then heat-treated for 5 minutes, a binder (main firing) was obtained. In this example, calcination was carried out. No pressure is applied in the two steps of the forming and the main firing. The adhesion of the bonded body obtained by the application is confirmed. Specifically, according to JIS Z-03918-5: 2003, the lead-free solder test method is the fifth solder joint. The method described in the "stretching and shearing test method" is a method in which the adherend (wafer) adhered to the substrate is pressed in the horizontal direction, and the force at which the adhesive surface is broken by the pressing force is measured. In this example, the test was carried out using a welding tester (Series 4〇〇〇) manufactured by DAGE Co., Ltd. The shear height was 150 μm, the test speed was 5 mm/min, and the measurement was carried out at room temperature. The rate was measured by the four-point probe method. As a result, the average shear strength between the five samples of Example 1 was 34 7 Mh, and the cv value (standard deviation/average value) indicating the change in adhesion was 141%. The test method is the direct measurement of the wire The force (N) depends on the value of the bonded area. Here, the "formatted value" is formed, and the force when the measured 099139896 201143960 is split is divided by the bonded area (this time 2 is 2 (mm) The value (MPa) of x2 (mm) = 4 mm) is set to be strong, and 'again. The following samples are also the same. &lt;Example 2 &gt; In addition to the paste of Example 1, it is changed to be covered. Sorbic acid glutinous rice;: sub-aggregate dry powder (average particle diameter: 60 nm) 45.0 g, metal % T,; &, &gt; 蜀 micron powder spherical silver particle powder (DWA manufactured by DOWA Electronics Co., Ltd.) 'Spherical silver powder: average particle size (D5G) 60 〇 nm) 45.0 g, octanediol (manufactured by Kyowa Fermentation Chemicals Co., Ltd.) 8.9 g, oxydiacetate 〇.i〇g (relative to the total paste weight 〇 And / /, and the wet dispersing agent of BEAULIGHT® LCA-25NH (Sanyo Chemical Co., Ltd.) 1.00 g (j 〇 % relative to the total paste weight) Step. 5 The average shearing strong sound system between samples 47.1 MPa' indicates that the cv value of the adhesion change is 7 8%, which is comparable to that of Example 1 and can be obtained with high adhesion strength. <Example 3> In addition to the paste composition of Example 2, 44.2 g of sorbic acid silver nanoparticle aggregate dry powder, spherical silver particle powder of metal micron powder 44 &amp; The procedure of Example 2 was repeated in the same manner as in the case of octanediol (manufactured by Kyowa Fermentation Chemical Co., Ltd.). The adhesive strength of the obtained adhesive and the CV value indicating the change were as shown in Table 1. &lt;Example 4&gt; The composition of the paste of Example 1 was changed to the same as the average particle size of the dry powder of the agglomerate dry powder, except for the average particle size of the dry powder of the agglomerate, 099139896 19 201143960 Repeat the steps of Example 。. The adhesion strength of the obtained adhesive and the CV value indicating the change are shown in Table 1. &lt;Example 5 &gt; In addition to the paste composition of Example 4, octyl glycol 9 was changed to 8.85 g of octanediol and 0.05 g of oxydiacetic acid (〇〇5% by weight relative to the total paste). Except for the rest, the steps of Example 4 were repeated. The bonding strength of the obtained joint and the CV value indicating the change are shown in Table 1. &lt;Example 6&gt; In addition to the paste composition of Example 4, 46.0 g of dry powder of sorbic acid-coated silver nanoparticle aggregates, spherical silver particle powder of metal micron powder, and octanediol ( The procedure of Example 4 was repeated in the same manner as in the case of 7. 〇g. The adhesive strength of the obtained adhesive and the CV value indicating the change are shown in Table 1. &lt;Example 7&gt; In addition to the paste composition of Example 4, it was changed to a silvery nanoparticle-containing aggregate powder of sorbic acid, 43. g, and a spherical silver particle powder 43 of a metal micron powder, such as The procedure of Example 4 was repeated except that the alcohol (Xihe Fermentation Chemical Co., Ltd. and 0.10 g of oxydiacetic acid (g. 1 G% relative to the total paste weight). The adhesive strength of the obtained adhesive and the change... The value is as shown in the following table. <Example 8> 099139896 20 201143960 In addition to the paste composition of Example 4, 44.2 g of dried silver nanoparticle particles of sorbic acid was added, and spherical powder of metal micron powder was used. Example 4 was repeated except that 44.2 g of silver particle powder, octyl alcohol (manufactured by Kyowa Fermentation Chemical Co., Ltd.), and 5 g of oxydiacetate (〇.10% based on the total paste weight) were used. The bonding strength of the obtained adhesive and the CV value indicating the change are shown in Table 1. Further, when the temperature of the main firing is set to 26 ° C, and heating is performed for 1 minute, the bonding strength is obtained. 22.1 MPa and a CV value of 22.4%. <Comparative Example 1 &gt; In addition to the paste composition of Example 1. Changed to silver granules of sorbic acid silver nanoparticle constitutive dry powder (average particle size: 6Gnm) 45.Gg, metal micron powder spherical silver particle powder (made by DOWA Electronics Co., Ltd. (10) small c spherical silver powder. The average particle diameter (D5 〇) 60 〇 nm) 45.0 g, and terpineol (structure isomer mixture / Wako Pure Chemical Industries, Ltd.) 9. 〇〇g, the rest of the example 1 is repeated Step 5. The average shear strength between the samples was 25 5 coffee, indicating that the CV value of the adhesive change was 30.6%, compared with the adhesive having a lower adhesive strength and a larger change than the example}. The terpineol was boiled at 219 ° C and the ignition point was 91 ° C. '&lt;Comparative Example 2&gt; In addition to terpineol (Compound isomer mixture / Wako Pure Chemical Industries, Ltd.) of Comparative Example 1. GGg was changed to 8.80 g of terpineol (manufactured by Structural Isomers / Wako Pure Chemical Industries, Ltd.) and 〇2〇g of oxydiacetate (g. 2% based on the total paste weight). The steps of the comparative example were repeated. The obtained 099139896 21 201143960 adhesive strength and the cv value indicating the change, as shown in Table 1 &lt;Comparative Example 3&gt; In addition to 9.00 g of the pine scale (structure isomer mixture / manufactured by Wako Pure Chemical Industries Co., Ltd.) of Comparative Example 1, it was changed to terpineol (structure isomer mixture / Wako Pure Chemical Industries Co., Ltd.) 8.90g, and the oxygen diacetic acid Q is called (G.1% relative to the total paste weight). The steps of the comparative example are repeated. The adhesive strength of the obtained adhesive and the cv value indicating the change are as shown in the table. &lt;Comparative Example 4&gt; The procedure of Example 4 was repeated except that the octanediol of Example 4 was changed to Pine (IV) (Structural Isomer Mixing / Wako Pure Chemicals 4 Co., Ltd.) . The adhesive strength of the obtained adhesive and the cV value indicating the change are shown in Table 1. [Table 1] Silver powder Solvent Oxyacetic acid (g) Sorbic acid (g) Micron powder (g) Terpineol (g): Boiling point 219 ° C Dispersant bonding strength (MPa) CV 60 nm lOOnm Octanediol (g): Boiling point 244 ° C (g) (%) Example 1 Example 2 tWmz - -- -- -- -- Example 4 ------------ 45.0 ........ .. 45.0 9.00 1.00 34.7 14.1 45.0 .......... 45.0 47.1 7 S 44.2 .......... 42.0 9 V 45.0 45.0 44.9 17 SX Court Example 5 ----- 1 45.0 50.0 6 S %ΡΜίβ. -- 46.0 49.6 10 S Example 7 Example 8 ^Comparative Example 1 tbKj'2 ........ 43.0 33.1 *&gt; -i 44.2 10.50 0.10 1.00 42.7 8.1 45.0 45.0 9.00 1.00 25.5 30.6 45.0 -______ .8.80 24.7 M 4 Comparative Example 3 tbfe^j*4 45.0 8.90 31.4 HI 0 9.00 1.00 29.8 12.8 099139896 22 201143960 If the comparison between Example 1 and Example 1 is made, the solvent is known. The effect of changing from terpineol (boiling point 219 C) to octanediol (boiling point 244). From this, it is known that the bond strength is high and the strength variation between the bonded samples is lowered. Further, when a part of octanediol is substituted with oxydiacetic acid, an adhesive having a high adhesive strength and a low variation can be obtained. This phenomenon can be known by comparison of Examples 丨 and 2. The comparison between Comparative Example 1 and Comparative Example 4 revealed an effect produced by changing the particle diameter (from 60 nm to 100 nm). Thereby, it was found that the obtained adhesive strength was slightly improved, and the change in strength between the bonded samples was lowered. In comparison with Comparative Example 4 and Example 4, it was found that the effect of changing the solvent was obtained, but the change in the strength between the bonded samples was the same, and the adhesive strength was remarkably improved. Further, when a part of octanediol is substituted with oxydiacetic acid, an adhesive having a relatively high bonding strength and a low variation can be obtained, which is known from the comparison of Examples 4 and 5. From the above, it is known that when the paste of the embodiment is used, it is possible to obtain an adhesive strength of up to 3 MPa or more and a change in adhesive strength of less than 20% irrespective of whether or not the paste is fired in nitrogen. This has a significant contribution to the improvement of product stability. Further, the viscosity measured in Example 5 was 71.5 MPa, and the viscosity measured in Example 7 was 2 8.5 Μ P a ', and it was found that a viscosity of a moderate viscosity can be provided in accordance with the composition of the metal. This phenomenon provides a paste having a viscosity suitable for various printing methods, and can be expected to be suitable for bonding for all uses. (Industrial Applicability) 099139896 23 201143960 It is known from the above that the bonding according to the present invention can be applied to a non-insulated semiconductor device, a bare crystal mounting assembly technique, and can also be applied to a power device (IGBT). , a rectifying diode, a power transistor, a power MOSFET, an insulated gate bipolar transistor, a thyristor, a gate-controlled switch thyristor, and a two-way thyristor bonding step. In addition, it can also be used as a surface treated with chromium. The glass bonding material can also be used as an electrode for an illuminating device using an LED, and an adhesive material to the frame. [Schematic Description of the Drawings] Fig. 1 shows the bonding strength (MPa) and the variation CV between samples in the examples and comparative examples ( Figure of %) 099139896 24

Claims (1)

201143960 七、申請專利範圍： 1. 一種黏合材料，係平均一次粒徑為1〜200nm，並含有： 由碳數8以下之有機物質所被覆的銀奈米粒子、以及沸點在 230°C以上的分散媒。 2. 如申請專利範圍第1項之黏合材料，其中，更進一步含 有平均粒徑0.5〜3.Ο/mi的銀粒子。 3. 如申請專利範圍第1或2項之黏合材料，其中，上述分 散媒係更進一步具有引火點在l〇〇°C以上的性質。 4. 如申請專利範圍第2或3項之黏合材料，其中，作為形 成上述黏合材料的成分，係更進一步含有具醚鍵結的物質。 5. 如申請專利範圍第4項之黏合材料，其中，上述具有醚 鍵結的物質係氧二乙酸(oxydiacetic acid)。 6. 如申請專利範圍第1至5項中任一項之黏合材料，其 中，被覆著上述銀奈米粒子表面的有機物中，至少一者係碳 數為6。 7. —種黏合方法，係相異二物質的黏合方法，包括有：於 黏合面上塗佈至少含有沸點在230°C以上的溶劑之黏合材 料的步驟（塗佈步驟）；在上述黏合材料上配置被黏合物的步 驟；在已配置上述被黏合物的狀態下，加熱至既定溫度的預 燒成步驟；以及加熱至較上述預燒成溫度更高溫度的主燒成 步驟。 8. 如申請專利範圍第7項之黏合方法，其中，上述預燒成 099139896 25 201143960 及上述主燒成的步驟係在惰性氣體環境下實施。 9.如申請專利範圍第7或8項之黏合方法’其中’上述主 燒成步驟係依200°C以上且500°C以下的溫度實施。 099139896 26201143960 VII. Scope of application: 1. A bonding material with an average primary particle size of 1 to 200 nm and containing: silver nanoparticles coated with an organic substance having a carbon number of 8 or less, and a boiling point of 230 ° C or higher. Disperse media. 2. The adhesive material according to claim 1, wherein the silver particles further have an average particle diameter of 0.5 to 3. Ο/mi. 3. The adhesive material according to claim 1 or 2, wherein the above-mentioned dispersing medium further has a property that the ignition point is above 10 °C. 4. The adhesive material according to claim 2 or 3, wherein the component forming the above-mentioned adhesive material further contains a substance having an ether bond. 5. The adhesive material of claim 4, wherein the ether bond material is oxydiacetic acid. 6. The adhesive material according to any one of claims 1 to 5, wherein at least one of the organic substances coated on the surface of the silver nanoparticles is at least 6. 7. A bonding method for bonding different materials, comprising: a step of coating an adhesive material having at least a solvent having a boiling point of 230 ° C or more on a bonding surface (coating step); and the above bonding material a step of disposing the adherend; a pre-firing step of heating to a predetermined temperature in a state in which the above-mentioned binder is disposed; and a main baking step of heating to a temperature higher than the pre-baking temperature. 8. The bonding method according to claim 7, wherein the pre-baking 099139896 25 201143960 and the main firing step are carried out under an inert gas atmosphere. 9. The bonding method according to claim 7 or 8, wherein the main firing step is carried out at a temperature of 200 ° C or more and 500 ° C or less. 099139896 26
TW099139896A 2010-06-11 2010-11-19 Low-temperature-sinterable bonding material, and bonding method using the bonding material TW201143960A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2010/059921 WO2011155055A1 (en) 2010-06-11 2010-06-11 Low-temperature-sintering bonding material and bonding method using the bonding material

Publications (1)

Publication Number Publication Date
TW201143960A true TW201143960A (en) 2011-12-16

Family

ID=45097684

Family Applications (2)

Application Number Title Priority Date Filing Date
TW099139896A TW201143960A (en) 2010-06-11 2010-11-19 Low-temperature-sinterable bonding material, and bonding method using the bonding material
TW100120513A TWI504704B (en) 2010-06-11 2011-06-13 Low temperature sintered bonding material and bonding method using the same

Family Applications After (1)

Application Number Title Priority Date Filing Date
TW100120513A TWI504704B (en) 2010-06-11 2011-06-13 Low temperature sintered bonding material and bonding method using the same

Country Status (6)

Country Link
US (1) US8641929B2 (en)
EP (1) EP2581156B1 (en)
KR (1) KR101709302B1 (en)
CN (1) CN102958631B (en)
TW (2) TW201143960A (en)
WO (2) WO2011155055A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI737643B (en) * 2015-11-16 2021-09-01 日商阪東化學股份有限公司 Bonding composition and electronic component assembly
US11784153B2 (en) 2014-04-04 2023-10-10 Kyocera Corporation Thermosetting resin composition, semiconductor device, and electrical/electronic component

Families Citing this family (37)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011007402A1 (en) * 2009-07-14 2011-01-20 Ｄｏｗａエレクトロニクス株式会社 Bonding material and bonding method each using metal nanoparticles
HUE039370T2 (en) * 2010-03-15 2018-12-28 Dowa Electronics Materials Co Bonding material and bonding method using same
WO2012059974A1 (en) * 2010-11-01 2012-05-10 Ｄｏｗａエレクトロニクス株式会社 Low-temperature sintering conductive paste, conductive film using same, and method for forming conductive film
CN103250236B (en) * 2010-11-22 2016-09-14 同和电子科技有限公司 Grafting material and conjugant and joint method
JP5750259B2 (en) * 2010-11-30 2015-07-15 ハリマ化成株式会社 Conductive metal paste
US20120291454A1 (en) * 2011-05-20 2012-11-22 Baker Hughes Incorporated Thermoelectric Devices Using Sintered Bonding
HUE039175T2 (en) * 2011-06-10 2018-12-28 Dowa Electronics Materials Co Bonding material and bonded object produced using same
KR101609497B1 (en) * 2012-01-20 2016-04-05 도와 일렉트로닉스 가부시키가이샤 Bonding material and bonding method in which said bonding material is used
JP2014047415A (en) * 2012-09-03 2014-03-17 Dowa Electronics Materials Co Ltd Silver powder for forming conductive film, conductive paste and method of forming conductive film
JP6179520B2 (en) 2012-09-05 2017-08-16 日立化成株式会社 Silver paste composition and semiconductor device using the same
JP6118192B2 (en) 2013-06-21 2017-04-19 Ｄｏｗａエレクトロニクス株式会社 Bonding material and bonding method using the same
TWI487446B (en) * 2013-06-21 2015-06-01 Nat Univ Chung Hsing A composite material having a composite structure
JP6095002B2 (en) * 2013-06-26 2017-03-15 三菱電機株式会社 Manufacturing method of high-frequency device
JP5664739B2 (en) * 2013-10-21 2015-02-04 トヨタ自動車株式会社 Metal nanoparticle paste
JP5738464B1 (en) * 2013-12-10 2015-06-24 Ｄｏｗａエレクトロニクス株式会社 Silver fine particle dispersion
WO2015098658A1 (en) * 2013-12-24 2015-07-02 Dic株式会社 Bonding material containing metal nanoparticles
JP5795096B2 (en) 2014-02-25 2015-10-14 田中貴金属工業株式会社 Silver paste excellent in low-temperature sinterability and method for producing the silver paste
JP6373066B2 (en) * 2014-05-30 2018-08-15 Ｄｏｗａエレクトロニクス株式会社 Bonding material and bonding method using the same
JP5992961B2 (en) * 2014-06-25 2016-09-14 Ｄｏｗａエレクトロニクス株式会社 Bonding material and bonding method using the same
JP6536581B2 (en) * 2014-07-22 2019-07-03 住友電気工業株式会社 Fine metal particle dispersion
CN107207911B (en) * 2015-01-29 2021-01-01 阪东化学株式会社 Composition for bonding and electronic component bonded body
WO2017033911A1 (en) 2015-08-25 2017-03-02 田中貴金属工業株式会社 Metal paste having excellent low-temperature sinterability and method for producing the metal paste
KR20180127313A (en) * 2016-03-30 2018-11-28 가부시키가이샤 오사카소다 Conductive adhesive
JP7007140B2 (en) * 2016-09-30 2022-01-24 Ｄｏｗａエレクトロニクス株式会社 Joining material and joining method using it
JP6631502B2 (en) * 2016-12-27 2020-01-15 日亜化学工業株式会社 Laser package manufacturing method
KR20190105610A (en) * 2017-01-11 2019-09-17 히타치가세이가부시끼가이샤 Copper pastes, assemblies and semiconductor devices for pressureless bonding
US11370066B2 (en) 2017-03-15 2022-06-28 Showa Denko Materials Co., Ltd. Metal paste for joints, assembly, production method for assembly, semiconductor device, and production method for semiconductor device
SG11201906718UA (en) * 2017-03-15 2019-10-30 Hitachi Chemical Co Ltd Metal paste for joints, assembly, production method for assembly, semiconductor device, and production method for semiconductor device
JP2018165387A (en) * 2017-03-28 2018-10-25 Ｄｏｗａエレクトロニクス株式会社 Bonding material and bonding body comprising the same
JP6561100B2 (en) * 2017-10-04 2019-08-14 Ｊｘ金属株式会社 Method for producing surface-treated copper fine particles
CN111295741B (en) * 2017-11-08 2023-09-01 株式会社力森诺科 Method for producing joined body and joining material
JP7093945B2 (en) * 2018-02-28 2022-07-01 公立大学法人大阪 Semiconductor chip joining method using nano-silver paste
JP6879512B2 (en) * 2018-09-20 2021-06-02 協立化学産業株式会社 Encapsulation composition
JP7170968B2 (en) * 2019-02-22 2022-11-15 株式会社大阪ソーダ Joining method using conductive adhesive
CN111843287A (en) * 2020-07-27 2020-10-30 中国科学院深圳先进技术研究院 Nano-silver soldering paste and preparation method and application thereof
CN112321306B (en) * 2020-11-08 2022-06-03 中民驰远实业有限公司 Magnesium binder and method for preparing refractory material by using magnesium binder
CN112475662A (en) * 2020-11-18 2021-03-12 中国科学院深圳先进技术研究院 Nano-silver solder paste, preparation method thereof and application of nano-silver solder paste in chip packaging interconnection structure

Family Cites Families (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003051562A1 (en) * 2001-12-18 2003-06-26 Asahi Kasei Kabushiki Kaisha Metal oxide dispersion
US20040245648A1 (en) * 2002-09-18 2004-12-09 Hiroshi Nagasawa Bonding material and bonding method
CN100519012C (en) * 2003-09-12 2009-07-29 独立行政法人产业技术综合研究所 Metal nano particle dispersion liquid capable of being sprayed in fine particle form and being applied in laminated state
US20050136638A1 (en) * 2003-12-18 2005-06-23 3M Innovative Properties Company Low temperature sintering nanoparticle compositions
CN100586613C (en) * 2004-06-25 2010-02-03 三菱麻铁里亚尔株式会社 Metal colloid particles, metal colloid and use of the colloid
JP5007020B2 (en) * 2004-12-20 2012-08-22 株式会社アルバック Method for forming metal thin film and metal thin film
JP4660780B2 (en) 2005-03-01 2011-03-30 Ｄｏｗａエレクトロニクス株式会社 Method for producing silver particle powder
JP4973830B2 (en) * 2005-07-29 2012-07-11 戸田工業株式会社 Conductive composition, conductive paste and conductive film
JP2007095525A (en) * 2005-09-29 2007-04-12 Tokai Rubber Ind Ltd Conductive paste
US8337726B2 (en) 2006-07-28 2012-12-25 Furukawa Electric Co., Ltd. Fine particle dispersion and method for producing fine particle dispersion
JP4279329B2 (en) * 2007-06-26 2009-06-17 古河電気工業株式会社 Fine particle dispersion and method for producing fine particle dispersion
US8277693B2 (en) 2006-07-28 2012-10-02 Furukawa Electric Co., Ltd. Method for producing fine particle dispersion and fine particle dispersion
JP4963393B2 (en) * 2006-10-03 2012-06-27 三ツ星ベルト株式会社 Low temperature firing type silver paste
CN101584010B (en) * 2007-01-09 2012-08-29 同和电子科技有限公司 Silver particle dispersion and process for producing the same
US7422707B2 (en) * 2007-01-10 2008-09-09 National Starch And Chemical Investment Holding Corporation Highly conductive composition for wafer coating
US20080272344A1 (en) * 2007-03-23 2008-11-06 Georgia Tech Research Corporation Conductive polymer composites
US7576434B2 (en) * 2007-06-26 2009-08-18 Intel Corporation Wafer-level solder bumps
JP4986745B2 (en) * 2007-07-05 2012-07-25 Ｄｏｗａエレクトロニクス株式会社 Silver paste
EP2208559B1 (en) 2007-10-24 2016-04-20 DOWA Electronics Materials Co., Ltd. Silver microparticle-containing composition, process for production of the composition, process for production of the silver microparticle, and paste containing the silver microparticle
WO2009090748A1 (en) 2008-01-17 2009-07-23 Applied Nanoparticle Laboratory Corporation Silver composite nanoparticle and process and apparatus for producing the same
JP5256281B2 (en) * 2008-03-18 2013-08-07 株式会社応用ナノ粒子研究所 Composite silver nanopaste, its production method and nanopaste bonding method
US8513534B2 (en) 2008-03-31 2013-08-20 Hitachi, Ltd. Semiconductor device and bonding material
JP5399110B2 (en) 2008-04-23 2014-01-29 トヨタ自動車株式会社 Bonding material and component calculation method for bonding material
KR101637200B1 (en) * 2008-08-11 2016-07-07 지호우 도쿠리츠 교세이 호진 오사카 시리츠 고교 겐큐쇼 Copper-containing nanoparticle and process for producing same
JP5431071B2 (en) * 2008-08-28 2014-03-05 三ツ星ベルト株式会社 Conductive substrate, precursor thereof, and production method thereof
US7935278B2 (en) * 2009-03-05 2011-05-03 Xerox Corporation Feature forming process using acid-containing composition
WO2011007402A1 (en) 2009-07-14 2011-01-20 Ｄｏｗａエレクトロニクス株式会社 Bonding material and bonding method each using metal nanoparticles
HUE039370T2 (en) 2010-03-15 2018-12-28 Dowa Electronics Materials Co Bonding material and bonding method using same
JP4928639B2 (en) 2010-03-15 2012-05-09 Ｄｏｗａエレクトロニクス株式会社 Bonding material and bonding method using the same

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11784153B2 (en) 2014-04-04 2023-10-10 Kyocera Corporation Thermosetting resin composition, semiconductor device, and electrical/electronic component
TWI737643B (en) * 2015-11-16 2021-09-01 日商阪東化學股份有限公司 Bonding composition and electronic component assembly

Also Published As

Publication number Publication date
WO2011155615A1 (en) 2011-12-15
CN102958631B (en) 2015-08-05
EP2581156B1 (en) 2016-06-01
TW201213473A (en) 2012-04-01
US20130081759A1 (en) 2013-04-04
KR101709302B1 (en) 2017-02-22
EP2581156A1 (en) 2013-04-17
WO2011155055A1 (en) 2011-12-15
KR20130101986A (en) 2013-09-16
EP2581156A4 (en) 2015-02-25
CN102958631A (en) 2013-03-06
TWI504704B (en) 2015-10-21
US8641929B2 (en) 2014-02-04

Similar Documents

Publication Publication Date Title
TW201143960A (en) Low-temperature-sinterable bonding material, and bonding method using the bonding material
TWI490170B (en) Adhesive material, adhesive method and adherend using the asme
JP4928639B2 (en) Bonding material and bonding method using the same
EP2455179B1 (en) Bonding material and bonding method each using metal nanoparticles
JP5824201B2 (en) Bonding material and bonding method using the same
JP6214600B2 (en) Joining materials and joints
TW201034776A (en) Silver microparticle powder, method for producing said powder, silver paste using said powder, and method for using said paste
JP5487301B2 (en) Low-temperature sinterable bonding material and bonding method using the bonding material